Emulsions mixed interfacial films

Seemingly, a minimum surfactant concentration is required to ensure the stability of the emulsion produced by dilution of the ECs. Mixed interfacial films with specific rheological properties are required for stabilisation of the emulsions. These films should provide high dilational viscoelasticity and they should prevent film thinning and drainage. This is discussed in more detail in Chapter 6. 

Addition of chemicals without careful consideration may break an emulsion. An emulsion prepared with ionic surfactants should not be mixed with chemically incompatible materials of opposite charge. The pH of the emulsion should be alkaline if the emulsion is made with alkali soaps. At an acidic pH, the carboxylate ion of the soap is converted to the carboxylic acid, which is not water-soluble and an emulsifying agent. An alkali-soap stabilized O/W-type emulsion may be inverted to a W/O-type emulsion by adding a divalent electrolyte. The carboxylate ion reacts with the divalent electrolyte to form an alkali earth soap that is an oil-soluble surfactant. Addition of a common electrolyte to an emulsion prepared with ionic surfactants suppresses the ionization according to the Le Chatelier rule (e.g., ammonium oleate and ammonium chloride). The presence of noninteractive electrolytes in the emulsions alters the polar nature of the interfacial film. For example, the... 

The formation and stabilization of 0/W emulsions prepared with mixed emulsifier systems has been extensively investigated. However, the mechanisms proposed differ greatly. One of the primary hypotheses attributes the enhanced stability to the formation of a molecular "complex" or layer at the oil/water interface (8-11). The mixture of emulsifier types increases the packing density of the adsorbed interfacial film. Several investigators have shown that more closely packed complexes produce more stable emulsions (9,12-14). Friberg, et al. (15-17) have attributed the enhanced stability of mixed emulsifier emulsions to the formation of liquid crystals at the oil/water interface, which reduce the van der Waals attractive forces. 

Emulsion stability is determined by the strength of the interfacial film and the way the adsorbed molecules in it are packed. If the adsorbed molecules in the film are closely packed, and it has some strength and viscoelasticity, it is difficult for the emulsified liquid droplets to break the film. In other words, coalescence is difficult. The emulsion is therefore stable. The molecular structure and the properties of the emulsifiers in the film affect the film s properties. The molecules in the film are more closely packed if the emulsifier has straight chains rather than branched chains. The film strength is increased if mixed emulsifiers are used rather than a single one. The reasons are that (1) the molecules in the film are closely packed, (2) mixed liquid crystals are formed between droplets, and (3) molecular complexes are formed in the interface by emnlsifier compositions. For example, an oil-soluble surfactant mixed with a water-solnble snrfactant works very well to stabilize emulsions (Kang, 2001). 

This method is particularly useful for the measurement of very low interfacial tensions (<10 mN m ) that are particularly important in applications such as spontaneous emulsification and the formation of microemulsions. Such low interfacial tensions may also be achieved with emulsions, particularly when mixed surfactant films are used. In this case, a drop of the less-dense liquid A is suspended in a tube containing the second liquid, B. On rotating the whole mass (see Figure 5.4) the drop of the liquid moves to the centre and, with an increasing speed of revolution, the drop elongates as the centrifugal force opposes the interfacial tension force that tends to maintain the spherical shape, which is that having a minimum surface area. 

An emulsion is a mixture of two or more immiscible liquids, whose interface is stabilized by an emulsifier. Essentially, emulsion contains oil and water. Emulsions are inherently thermodynamically unstable system, often recognizable by their cloudy or white appearance since the substances do not mix homogenously. The mixed substances often separate due to reduction in the interfacial energy after a period of time. The possible mechanism of destabilization can be creaming, flocculation, or coalescence. The emulsions possess kinetic stability, which is lost after a period of time. The kinetic stability is associated with the presence of interfacial film around the dispersed droplets at the oil/water interface by the emulsifier. The interfacial film increases the interfacial viscosity, which retards the coalescence of the droplets. ... 

Emulsion droplets are normally stabilized by enhancing the mechanical strength of the interfacial film formed around the oil droplets (38). by steric stabilizaticm effects, and/or by the presence of charged surfactants which create an electrostatic barrier. The stabilizing factor of the latter is the electrostatic repulsimi of similarly charged droplets. The emulsion stability can be considerably improved with the use of mixed emulsifying agents (39). 

It has long been argued that interfacial rheology, namely interfacial viscosity and elasticity, play an important role in emulsion stability. This is particularly the case with mixed surfactant films (which may also form liquid crystalline phases) and polymers such as hydrocolloids and proteins that are commonly used in food emulsions. 

Correlation of emulsion stability with interfacial rheology 5.9.1.7.1 Mixed surfactant films... 

It was observed that the titration of a coarse emulsion by a coemulsifier (a macromonomer) leads in some cases to the formation of a transparent microemulsion. Transition from opaque emulsion to transparent solution is spontaneous and well defined. Zero or very low interfacial tension obtained during the redistribution of coemeulsifier plays a major role in the spontaneous formation of microemulsions. Microemulsion formation involves first a large increase in the interface (e.g., a droplet of radius 120 nm will disperse ca. 1800 microdroplets of radius 10 nm - a 12-fold increase in the interfacial area), and second the formation of a mixed emulsifier /coemulsifier film at the oil/water interface, which is responsible for a very low interfacial tension. 

Low internal phase emulsions typically result when high shear conditions are used for emulsification, while low shear mixing can lead to high internal phase, or concentrated, emulsions [435]. There are several conditions needed to form a concentrated emulsion. Low shear mixing is required while the internal phase is slowly added to the continuous phase, and the surfactants used to create the emulsion need to be able to form elastic films [435—438]. The formation of concentrated emulsions has also been linked to surfactant-oil phase interactions [436] and therefore the oil-water interfacial tension and the potential for surfactant-surfactant interactions [439]. 

Hallworth and Carless (1 ) discuss several possibilities for the effect of light liquid paraffin on the stability of emulsions with light petroleum or chlorobenzene as the main components. They seem to prefer an explanation previously advanced by them and several other authors for the effect of fatty alcohol, namely that the increased stability is due to the formation of an interfacial complex between the additive and sodium hexadecyl sulphate. The condenced mixed film will resist coalescence primarily by virtue of its rheological properties. With mixed films of the present type, the importance of the film viscoelasticity lies in its ability to maintain electrical repulsion between approaching droplets by preventing lateral displacement of the adsorbed ions. The effective paraffinic oil has chains at least as long as those of the alkyl sulphate and will be associated by van der Waals forces with the hydrocarbon chain of the alkyl sulphate at the interface. 

Fluorinated surfactants (or fluorosurfactants, i.e., surfactants with hydrophobic tails comprising a fluorocarbon moiety) provide an alternative means of achieving extremely stable PFC emulsions, as they can provide very low PFC/water interfacial tensions [cr , another factor in Eq. (2)]. d s yet, this option has not been developed, in part because of the added cost involved in the evaluation for approval of a novel active excipient. A further means of effectively increasing the stability of EYP-based PFC emulsion consists of supplementing standard phospholipids with mixed fluorocarbon-hydrocarbon diblock compounds, such as 14 or 15. Such diblocks, which have fluorophilic-lipophilic amphiphilic properties, are expected to improve the adhesion of the phospholipid film onto the PFC droplet. 

Monolayer techniques were used to characterize the interfacial properties of the resultant Fractions. Fraction I contained highly cohesive complexes that did not unfold at the interface and had an average diameter of 9.1 nm. These particles are thought to represent submicelles, previously identified in micelle formation. Fraction II showed interfacial properties that are characteristic of spread casein monomers, and contained mainly a -casein. The results are discussed in relation to casein interactions and micellar formation. Mixed monolayers of sodium caseinate/glyceride monostearate (NaCas/GMS) were also examined at different composition ratios. The results show that for low surface pressures (0-20 mNm ), there is a condensation ascribable to hydrophobic interactions in the mixed film. At high surface pressures, the hydrophobic interaction is modified and the protein is expelled from the monolayer into the subphase. These results are discussed in relation to emulsion stability. 

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